Вы находитесь на странице: 1из 42

Pale

yellow

Yellow
orange
41

green


Electronic Spectra
CoF6– Co(NH3)63+ Co(CN)3+
6
of Transition Metal
High spin Low spin Low spin Complexes
4.1. INTRODUCTION
Electronic spectra of transition metal complexes help us to gain an insight into the structure and
bonding in these compounds. A very exciting characteristic of transition metal complexes is that they
exhibit colours of varying intensity throughout the visible range. A blue solution of copper sulphate
becomes dark blue on addition of ammonia solution. Perhaps the nature of the ligand has something
to do about it. The stronger NH3 ligands replace the H2O ligands. Sometimes the same metal displays
different colours even with the same ligands in different crystal fields. For example, cobalt (II) forms
pink [Co(NH3)6 ]2+ in octahedral field but blue [CoCl4]2– in tetrahedral field. Blood that flows in
our body is red because of complexation of heme group with iron. Prussian blue which has been used
as a dye since olden times is a coordination compound of iron.
It has been established that colour of complex compounds is because of d – d transitions. The
electrons are excited from the lower d-orbitals to the higher d-orbitals. Energy from the visible range
is absorbed in these radiations. Rest of the radiations (energy) are transmitted. It is the transmitted
radiations that form the colour of the substance. It is important to remember that the colour of a
substance is not the radiations that are absorbed but the radiations that are transmitted. We know
that visible (white) light consists of different colours like violet, indigo, blue, green, yellow, orange
and red. If one or more of the radiations are absorbed by a substance, the resultant of the rest of the
colours will be the colour displayed by a substance. If a substance does not absorb any colour, it looks
white. If it absorbs all the colours, it looks black.

4.2. BASIS OF ELECTRON–ABSORPTION


In tetrahedral complexes, the electron gets excited from lower set of d-orbitals to higher set of
d-orbitals when visible light is incident on them. As a result of transition some selected wavelength
of visible light corresponding to energy difference between t 2g and e g levels is absorbed. The
transmitted light gives colour to complexes. This is explained with the help of the following diagram.
It may be recalled that degenerate d-orbitals split into two sets of d-orbitals, t2g and eg in the presence
of ligands in octahedral field.

84

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 85

The amount of energy absorbed can be given as :


hc
E = hv =

where c is the velocity of light and h is Planck’s constant.
The extent of intensity of absorption of light of a particular wavelength (or frequency) by a
species in solution can be obtained by Beer-Lambert law. If light of intensity, I0 at a given
wavelength passes through a solution, the light transmitted with intensity, I may be measured by a
suitable detector. According to Beer–Lambert, law, the light transmitted and incident light are related
as :
I0
log = A = lc
I
where A = absorbance
c = molar concentration of absorbing species
 = constant known as molar extinction coefficient.
It is also called molar absorptivity (L mol–1 cm–1)
l = path length through solution (in cm).
I0
The term log represented by A is known as absorbance (or optical density). The molar
I
absorptivity is a characteristic property of the species that is absorbing the light and is highly
dependent on wavelength. A plot of molar absorptivity versus wavelength gives a spectrum
characteristic of the molecule or ion. This spectrum provides valuable information about the structure
and bonding of the molecule or ion.

4.3. TERM SYMBOLS AND LS COUPLING


The complete description of the electrons in an atom can be obtained in terms of four quantum
numbers. These four quantum numbers are :
(i) Principal quantum number, n. It determines the main energy level or shell in which the
electron is present. It can have whole number values as :
n = 1, 2, 3, 4...........
(ii) Angular quantum number, l. It is related to the angular momentum of the electron. In
multi-electron atoms (an atom having a number of electrons) the energy besides depending upon n,
also depends on l. Corresponding to each value of n, there are n possible values of l as :
l = 0, 1, 2, 3 ........... (n – 1)
These various values of l (called subshells) are designated as s, p, d, f ..........
Value of l 0 1 2 3 4 and so on
Designation s p d f g and so on
(iii) Magnetic quantum number, m. It refers to the different orientations of the orbitals in
space. For a given value of l, m can have (2l + 1) values as :
m = – l, – (l – 1) .......... 0 .......... + (l – 1), + l
Thus if l = 1, m will have 3 values viz. – 1, 0, + 1.
If l = 2, m will have 5 values viz., – 2, – 1, 0, + 1, + 2.

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
86 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

(iv) Spin quantum number, s. This describes the spin orientation of the electron. Since the
electron can spin only in two ways : clockwise and anticlockwise, s can have only two values :
+ 1 2 and  1 2 . The values may also be indicating by arrows pointing up () and down ()
respectively. It determines the spin angular momentum.
The distribution of electrons in different levels in an atom is known as electronic configuration.
The filling of orbitals is governed by the three well known rules.
1. Aufbau principle. Electrons enter the orbitals of lowest energy first and subsequent electrons
are filled in increasing order of energy (1s, 2s, 2p, 3s, 3p, 4s, 3d ...........).
2. Paulis exclusion principle. No two electrons in an atom can have the same value for the
four quantum numbers.
3. Hund’s rule. When several orbitals of the same energy are available (degenerate orbitals),
the electrons tend to remain unpaired as for as possible i.e., the electrons tend to retain parallel spins
as much as possible, on energy consideration.
The electronic configuration of the outershell is generally represented by a box diagram. The
boxes represent orbitals and electrons are indicated by arrows. For example, the s-orbitals are
indicated by a single box, the p-orbitals are indicated by three boxes, one each for the px , py and pz
orbitals.
Similarly the d-orbitals are represented by five boxes, one each for dxy , dyz , dzx , d x2  y 2 and
d as shown below :
z2
One s-orbtials

Three p-orbitals px py pz

Five d-orbitals d xy d yz d zx d d
x2  y2 z2

The f-orbitals are represented by seven boxes. A spin quantum number of  1 2 is indicated by
the arrow  and  1 2 by the arrow . When only one electron is present in a degenerate energy level
such as s, p or d subshell, it can occupy any one of the possible arrangements.
However, for atoms with more than one electron in degenerate orbitals, several different
arrangements are possible which may not have same energy. For example, carbon has the electronic
configuration as :
1s2 2s2 2p2
It has two electrons in 2p subshell. There are 15 different arrangements in which the two
electrons can be added to a set of degenerate three p-orbitals having l = + 1, 0, – 1 corresponding
to px, py and pz
l= +1 0 –1 + 1 0 –1 +1 0 –1 +1 0 –1 +1 0 –1

         
l= +1 0 –1 +1 0 –1 +1 0 –1 +1 0 –1 +1 0 –1

         
l= +1 0 –1 +1 0 –1 +1 0 –1 +1 0 –1 +1 0 –1

      

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 87

Some of these arrangements would be of higher energy and some would be degenerate because
of different inter electronic-repulsions. The inter-electronic repulsions for the arrangement where two
electrons are present in the same orbital are higher than for those arrangements in which they are
present in different orbitals. Consequently, the energy for the former arrangements would be larger
than for those for the latter arrangements. Thus, unlike in a single electron system, many more energy
states exist in multielectron systems. These different arrangements may be grouped into different sets
of degenerate energy states. Furthermore, spin angular momentum (s) and orbital angular momentum
(l) of the electrons may interact or couple to give a resultant angular momentum for the entire multi-
electron atom. The resultant angular momentum and the energy of the system is expressed in a term
symbol. Thus,
term symbols are used to indicate the electronic configuration and the resultant angular
momentum of an atom.
The term symbol for a particular atomic state is expressed as :
2S + 1
LJ
where S = total spin angular quantum number
L = total orbital angular quantum number
J = total angular momentum quantum number
(2S + 1) is called the spin multiplicity of the state (arrangement)
Just as we have the symbols s, p, d, f ........... for l = 0, 1, 2 , 3 ..........., the different values of
L are designated by S, P, D, F, G, H, I, etc. Thus the state S represents L = 0, P represents L = 1 and
so on
L 0 1 2 3 4 5 6 7
State S P D F G H I K
It may be noted that we don’t assign the state J because this letter is used to represent another
quantum number viz. total angular momentum quantum number.
The total angular momentum, J of an atom can be generally determined by two methods. These
are :

1. LS or Russell Saunders Coupling


2. JJ Coupling
LS or Russel Saunders Coupling scheme is applicable to systems in which spin orbital
interactions are relatively small. In this scheme, the individual orbital angular momenta of the
electrons couple (or interact) to give a resultant angular momentum represented by the quantum
number, L for the state. The individual electron spin momenta also couple to give a resultant spin
momentum described by the quantum number, S. The L and S values together determine the total
angular momentum, J which can take quantized positive values ranging from | L – S | to | L + S |.
| | indicates the absolute value of | L – S | and no regard is paid to the sign, so that J is always  0.
Thus, the range of J can be written as
J = | L + S |, | L + S – 1 | ......... | L – S |

Rules for determining the term symbol according to L – S coupling scheme


The steps involved in determining the term symbol according to L – S coupling scheme are
as under :

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
88 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

A. Determining total spin angular momentum (ss coupling)


For a single electron we know spin quantum number, ms = 1 2 . When two or more electrons
are present in subshell, then their magnetic fields couple to produce
resultant spin quantum numbers, S. The resultant spin quantum
number is calculated as :
S = (s1 + s2), (s1 + s2 – 1) ......... | s1 – s2 |
where the modulus sign | | indicates the positive value.
For example, for a subshell having two electrons (p2 or d2) :
S = 1 2  12 , 1 2  12 – 1
or S = 1, 0
The spin multiplicity is given by the relation 2S + 1 and is
written in the upper left hand corner of the term symbol for the state. Henry Norris Russel
Spin multiplicity of 3 represents triplet state and a spin multiplicity of 1 represents a singlet
state.
Unpaired S Spin multiplicity Name of state
electrons (2S + 1)
0 0 1 Singlet
1
1 2
2 Doublet
1  1
2 2 2
=1 3 Triplet
1  1  1  1 12
3 2 2 2
4 Quartet
1  1  1  1
4 2 2 2 2
=2 5 Quintet

It is clear from above that the spin multiplicity (2S + 1) is always one more than the
number of unpaired electrons.

B. Determination of resultant orbital angular momentum (ll Coupling)


When two electrons with angular quantum number l1 and l2 interact, the resultant angular
quantum number, L are given by the relationship :
L = (l1 + l2), (l1 + l2 – 1), (l1 + l2 – 2) .......... | l1 – l2 |
where the modulus sign | | indicates the positive value.
For example, for a p subshell having two electrons (as in carbon).
l1 = 1 and l2 = 1 so that
L = (1 + 1), (1 + 1 – 1), .......... (1 – 1)
= 2 1 0
States D P S
Therefore, p2 electrons (as in carbon) will be represented by three energy states S, P and D
corresponding to L = 0, 1 and 2 respectively.
Similarly, for d2 configuration, the energy states can be obtained as under :
l1 = 2 and l2 = 2

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 89

L = (2 + 2), (2 + 2 – 1), 2 + 2 – 2, (2 + 2 – 3), 2–2


= 4 3 2 1 0
States G F D P S
Thus, d2 configuration is represented by five energy S, P, D, F and G corresponding to
L = 0, 1, 2, 3 and 4 respectively.

C. Spin-orbital or L – S Coupling
The magnetic effects of the resultant angular momentum, L and the resultant spin moment S
couple together to give new quantum number J called the total angular quantum number. J values
can be obtained by the vectorial combination of L and S by the coupling scheme called Russell
Saunders or LS coupling. The J can acquire all quantized positive values in the range | L – S | to
| L + S | as :
J = (L + S), (L + S – 1), (L + S – 2) .......... | L – S |
The J values are separated by 1. The modulus sign | | indicates the absolute value of | L – S |
so that J  0.
The J value is written as a subscript in the term symbol.
We shall illustrate these rules by taking the examples of p2 and d2 configurations :

p2–Configuration
Step 1
For the two p-electrons l1 = 1 and l2 = 1
L = (1 + 1), (1 + 1 – 1), (1 + 1 – 2)
= 2, 1, 0
States D, P, S
It may be noted that the last value of L can also be obtained by | l1 – l2 | i.e.
1–1=0
The energy states are S, P and D.
Step 2
For two electrons,
1 1 1 1
S = ( 2
 2
), (  2
 2
– 1),
= 1, 0
1  1
It may be noted that the second value of S can also be obtained by | s1 – s2 | or 2 2
=0
The spin multiplicity (2S + 1) is :
For S = 1, spin multiplicity = 3 (Triplet)
For S = 0, spin multiplicity = 1 (Singlet)
Therefore, we have six states corresponding to states D, P and S and corresponding to spin
multiplicity 3 and 1 each which can be written as
3S, 3P, 3D, 1S, 1P and 1D.

Step 3
Calculation of J values;
(a) When L = 2, 1 and 0 and S = 1

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
90 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

(i) When L = 2, S = 1 i.e. 3D state


J = (2 + 1), (2 + 1 – 1), (2 + 1 – 2)
= 3, 2, 1
We cannot have J = 0 because the range J is from | L + S | to | L – S | i.e.
| 2 + 1 | to | 2 – 1 | i.e. 3 to 1
 Complete spectroscopic term symbols 2S + 1LJ
3D , 3D and 3D .
3 2 1
3
(ii) When L = 1 and S = 1 i.e. P state.
J = (1 + 1), (1 + 1 – 1), (1 + 1 – 2)
= 2, 1, 0
 Complete spectroscopic terms are :
3P , 3P and 3P .
2 1 0
(iii) When L = 0 and S = 1 i.e. 3S state
J = 1+0
= 1
We cannot have J = 0 because the range for J is from | L + S | to | L – S |
i.e. | 0 + 1 | to | 0 – 1 | i.e. 1 only
Complete spectroscopic term symbol 2S + 1LJ is 3S1
(b) When L = 2, 1 and 0 and S = 0
(i) When L = 2 and S = 0 i.e. 1D states
J
J = 2+0
= 2
J cannot have values 1 and 0 because the range is
from | 2 + 0 | to | 2 – 0 | i.e. 2 only
L
 Complete spectroscopic term symbol, 2S + 1LJ is
1D
2
(ii) When L = 1 and S = 0 i.e. 1P states
J = 1+0 l1
= 1.
J cannot have the value 0 because J ranges between | l2
S
1 + 0 | and | 1 – 0 | i.e. 1 only s1
 Complete spectroscopic term is 1P1
(iii) When L = 0 and S = 0 i.e. 1S state
s2
J = 0
Russel Saunder’s Coupling
 Complete spectroscopic term is 1S0
Thus, the total term symbols for p2 configuration are :
3D , 3D , 3D , 3P , 3P , 3P , 3S , 1D , 1P and 1S .
3 2 1 2 1 0 1 2 1 0
Each of these value corresponds to an electronic arrangement.
All the spectroscopic terms derived for a p2 configuration would occur for an excited state of
carbon (1s2 2s2 2p1 3p1) in which the two p electrons belong to different subshells. However, in the
ground state of carbon atom (1s2 2s2 2p2) the number of states is restricted by the Pauli exclusion
principle which states that no two electrons in the same atom can have the same value for all the
four quantum numbers.

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 91

In the ground state configuration of carbon, both the p electrons have the same value of n and
l, (n = 2 and l = 1), so they must differ in at least one of the remaining quantum numbers m or s.
Pauli’s exclusion principle restricts the number of terms from 1S, 1P, 1D, 3S, 3P, 3D to 1S, 3P and
1D only. Table 4.1 gives all the fifteen allowed values of M and M for the p2 configuration (which
L S
do not violate Pauli’s principle). It can be shown that these 15 arrangements can be represented by
only three terms 1S, 3P and 1D by taking suitable values of ML (2L + 1) and MS (2S + 1) as illustrated
below :
For p electrons, the angular quantum number l = 1 and magnetic quantum number m has values
from + l ............ 0 ............ – l, giving in this case values of m = 1, 0 , – 1. The spin quantum number
has values of  1 2 and  1 2 for each value of m. The total spin quantum numbers and total orbital
quantum numbers can be obtained by adding the appropriate values of m and l as explained earlier :
ML has values from + L ............ 0 ............ – L (a total of 2L + 1 values).
MS has values from + S ............ 0 ............ – S (a total of 2S + 1 values).
The L and S quantum numbers which are associated with each electronic configuration or term
symbol can be obtained from ML and MS quantum numbers as shown in Table 4.1. The values of
MS and ML can be obtained by adding the appropriate values of ms and n
MS =  ms and ML =  m
Table 4.1. Allowed values of ML and MS for p2 configuration
S.No. m=+1 0 –1 MS ML Term
ms ml symbol
1D
1.  0 2

2. 0 –2 1D

3.  0 0

 3P, 1D, 1S
4.   0 0

5.   0 0

6.   0 1 

 3P, 1D
7.   0 1 

8.   0 – 1 
 3P, 1D
9.   0 – 1 

10. 1 1 3P
 
11. 1 0 3P
 
12. 1 –1 3P
 
13. –1 1 3P
 
14. –1 0 3P
 
15. –1 –1 3P
 

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
92 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

Steps to assign spectroscopic term symbol


(i) Write the different values of MS and ML for the given configuration of valence shell
electrons.
(ii) Select the maximum MS value and then the maximum ML value associated with it. In the
present case, it is MS = 1 and ML = 1 (S.No. 10 in Table). This corresponding to a group of terms
where L = 1 and S = 1. Since L = 1, it must be a P state and since S = 1, the multiplicity (2S + 1)
= 3 so that it is a 3P (triplet P) state.
Now if L = 1, ML may have values + 1, 0 and – 1 and if S = 1, MS may have the value + 1, 0,
and – 1. It gives rise to nine combinations of ML and MS values as given below
ML = + 1 MS = + 1, 0, – 1
ML = 0 MS = + 1, 0, – 1
ML = – 1 MS = + 1, 0, – 1
3
Thus we assign the symbol P to nine of the allowed values in Table 4.1
(iii) From the remaining MS and ML values, we pick out the next maximum MS and ML value.
It is MS = 0 and ML = 2. Since L = 2, it must be a D state and S = 0 gives a multiplicity of 2S + 1
= 1, so it is a 1D (singlet D) state.
With L = 2, ML may have values of + 2, + 1, 0, – 1 , – 2 and if S = 0, MS has only one value,
i.e., 0.
We get the following five combinations of ML and MS which can be assigned 1D term symbol.
ML = + 2 MS = 0
ML = + 1 MS = 0
ML = + 0 MS = 0
ML = – 1 MS = 0
ML = – 2 MS = 0
So far, we have considered 14 combinations, 9 of P and 5 of 1D. The remaining configuration
3

corresponds to MS = 0 and ML = 0. This gives a singlet S state 1S.


Thus we can say that all the 15 electronic arrangements can be represented by three
states:
1S, 3P and 1D.

Derivation of Term Symbols for a d2 configuration


For d electrons, the subsidiary quantum number l is 2. For two d-electrons having l1 = 2 and
l2 = 2, the values of L can be obtained as
L = (2 + 2), (2 + 2 – 1), (2 + 2 – 2), (2 + 2 – 3), (2 + 2 – 4)
4 3 2 1 0
These values of L represent S, P, D, F and G states corresponding to L = 0, 1, 2 , 3 and 4
respectively.
Values of S can be obtained as
S = (  1 2  1 2 ), ( 1 2  1 2 – 1)
Therefore, the values of spin multiplicity, (2S + 1) are 3 and 1. So we have 1S, 1P, 1D, 1F, 1G and
3S, 3P, 3D, 3F and 3G. There are 45 ways in which two d-electrons may be arranged without violating
the Pauli exclusion principle. These arrangements are given in Table 4.2.

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 93

However, these arrangements can be represented by only five states; 1S, 3P, 1D, 3F and 1G. This
can be seen in a similar way as for p2 electrons.
(i) Maximum value of MS = 1 and the maximum value of ML corresponding to this MS is 3
(Refer to S.No. 2 in Table 4.2). Since this corresponds to L = 3, it represents F state. This occurs
with MS = + 1, 0, – 1 suggesting a triplet F state i.e. 3F.
Now there are 21 combinations of ML and MS values associated with 3F term for L = 3 as
shown below :
ML = + 3 MS = + 1, 0, – 1
ML = + 2 MS = + 1, 0, – 1
ML = + 1 MS = + 1, 0, – 1
ML = 0 MS = + 1, 0, – 1
ML = – 1 MS = + 1, 0, – 1
ML = – 2 MS = + 1, 0, – 1
ML = – 3 MS = + 1, 0, – 1
(ii) The next highest unassigned MS is 0. The corresponding value of ML is 4 (Sr. No. 1 in the
Table 4.2). This corresponds to G state. Since MS = 0, S must be 0 and it is a singlet G term, 1G.
Now, if L = 4, ML can have the values + 4, + 3, + 2, + 1, 0, – 1, – 2, – 3, – 4. If S = 0, MS =
0 (only one value).
Thus, there are nine configurations associated with this term, 1G.
(iii) For ML value of 2, maximum value of MS = 0. This ML = 2 corresponds to D state. Since
MS = 0 for this state, it corresponds to spin multiplicity of 1 suggesting the state 1D.
Table 4.2. Allowed values of MS and ML for the d2 configuration
S.No. m = +2 +1 0 –1 –2 MS = ms ML = ml Term symbol

1. 0 4 1G


2. 1 3 3F
 

3.   0 3 
1G, 3P

4.   0 3 

5. –1 3 3F
 

6. 1 2 3F
 

7.   0 2

 1G, 3F, 1D
8.   0 2

9.  0 2 

10. –1 2 3F
 

11.   1 1
3F, 3P

12.   1 1

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
94 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

S.No. m = +2 +1 0 –1 –2 MS = ms ML = ml Term symbol

13.   –1 1
 3F, 3P
14.   –1 1

15.   0 1

16.   0 1 


17. 0 1 1G, 3F, 1D, 3P
 


18.   0 1 

19.   1 0
3F, 3P

20.   1 0

21.   0 0

22.   0 0

 1G, 3F, 1D, 3P, 1S
23.   0 0

24.   0 0


25.  0 0

26.   –1 0
3F, 3P

27.   –1 0

28.   0 – 1

29.   0 – 1


30. 0 – 1 1G, 3F, 1D, 3P
 


31.   0 – 1

32.   1 – 1
3F, 3P

33.   1 – 1

34.   –1 –1
 3F, 3P

35.   –1 – 1

36. 1 –2 3F
 

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 95

S.No. m = +2 +1 0 –1 –2 MS = ms ML = ml Term symbol

37.   0 – 2

38.   0 – 2  1G, 3F, 1D


39.  0 – 2 

40. –1 –2 3F
 

41. 1 –3 3F
 

42.   0 – 3
1G, 3F

43.   0 – 3

44. –1 –3 3F
 

45. 0 –4 1G

Now, if L = 2, ML may have values + 2, + 1, 0, – 1 , – 2
and if S = 0, MS may have (only one value) that is 0.
We can assign this state to five of the combinations (Table 4.2).
(iv) We have some combinations, in which maximum MS = 1 and the maximum ML value
associated with it is 1. Therefore, it corresponds to a P state. Since S = 1, spin multiplicity is 2 × 1
+ 1 = 3. So it corresponds to a triplet P state, 3P.
Now, if L = 1, ML may have values + 1, 0, – 1 if S = 1, MS may have the values + 1, 0, – 1.
Thus, there are nine combinations of ML and MS values :
ML = + 1 MS = + 1, 0, – 1
ML = 0 MS = + 1, 0, – 1
ML = – 1 MS = + 1, 0, – 1
These 9 combinations can thus be assigned the state 3P.
(v) We have considered 21 + 9 + 5 + 9 = 44 combinations so far and only one combination is
left. Combination of MS = 0 and ML = 0 is left. Here L = 0 and it corresponds to singlet. The term
(state) 1S can be assigned to it.
Since L = 0 and S = 0, it corresponds to only one term.
Thus, all the allowed values of ML and MS for d2 configuration may be represented by
1S, 3P, 1D, 3F and 1G states.

Derivation of the Term Symbol for closed shell configuration


If a subsell is completely filled with electrons for example p6 or d10 arrangements, then the
values of both MS and ML come out to be zero.
+1 0 –1 MS ML
p6    0 0
+2 +1 0 –1 –2
d10      0 0

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
96 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

Since ML = 0, so L = 0 and it corresponds to ‘S’ state. Since MS = 0 and so S = 0 and therefore,


multiplicity is 2S + 1 = 1.
Thus, a closed shell of electrons always produces a singlet S state, 1S0.

4.4. SPECTROSCOPIC GROUND STATES


The different terms in an atom as obtained above can be arranged in order of energy and the
ground state term is identified on the basis of Hund’s rules. The following rules determine the order
of energy for different terms.
1. The terms are arranged depending upon their spin multiplicities, i.e. their S-values. The most
stable state has the highest S-value and stability decreases as the value of S decreases.
In other words the most stable state (ground state) has maximum unpaired electrons. This
gives the minimum electrostatic repulsion and hence the lowest energy.
2. For a given value of S, the state with the highest value of L is the most stable state. This
means that if two or more terms have the same value of S (same spin multiplicity), the state
with highest value of L will have the lowest energy.
3. For terms having same S and L values,
the term with smallest J value is most stable if the subshell is less than half filled
the term with maximum J value is most stable if the subshell is more than half filled.
We shall apply these rules to the terms derived for p2 and d2 configurations.

p2 configuration
The terms for ground state of p2 configuration are 3P, 1D and 1S. We have to find out the ground
state out of these. The most stable state out of these three states is 3P because its multiplicity is
maximum. So, 3P is the ground state (most stable state).
Out of 1D and 1S (both having the same value of S), 1D is more stable because it has a higher
value of L = 2.
No the triplet P state has three terms 3P2, 3P1 and 3P0. According to third rule, 3P0 is the lowest
energy term (because 2p2 configuration of carbon is less than half filled) and these terms may be
arranged in increasing order of energy as
3P < 3P < 3P
0 1 2
The different terms of carbon are arranged in the increasing order of energy in Fig. 4.1. This
order corresponds to experimentally measured energies shown in brackets.
1 1
S S0 –1
(259.0 kJ mol )
1 1
D D2 –1
(122.0 kJ mol )
ENERGY

Carbon
1s2, 2s2, 2p2
(Ground state) 3 –1
P2 (0.52 kJ mol )
3
P 3 –1
3 P1 (0.20 kJ mol )
P
0 3
P0 (0)
Fig. 4.1. Splitting of terms in ground state of carbon

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 97

d2 configuration
The terms for ground state of d2 configuration (e.g. of V3+ ion) as derived earlier are 1S, 3P,
1D, 3F and 1G.
Let us arrange them in increasing order of energy and determine the ground state.
According to rule 1, the stable state corresponds to highest multiplicity. In this case both 3P
and F have common multiplicity 3 (or S = 1). Applying rule 2, 3F term wil be more stable because
3

it has higher value of L i.e. 3 (3P state has L = 1). So energies of these two states are arranged as
3F < 3P.

The remaining three states have same spin multiplicity = 1 (i.e. S = 0). These can be arranged
according to L values as :
1G < 1D < 1S.

The splitting of terms in ground state of d2 configuration are shown in Fig. 4.2. It may be noted
that the two triplet states 3F (3F2, 3F3, 3F4) and 3P (3P0, 3P1, 3P2) can further split and arranged
according to the rule 3 as shown in Fig. 4.2.

Fig. 4.2. Splitting of terms in d2 configuration


The ground state terms of d1 to d10 electronic configurations (without splitting) are given in
Table 4.3 :

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
98 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

Table 4.3. Ground state terms for d1 to d10 configurations


Configuration Ground state term Example
d1 2D Ti3+
d2 3F V3+
d3 4F Cr3+
d4 5D Cr2+
d5 6S Mn2+
d6 5D Fe2+
d7 4F Co2+
d8 3D Ni2+
d9 2D Cu2+
d10 1S Cu+

HOLE FORMULATION (FORMULISM)


If a subshell is more than half full, it is more convenient to find out the terms by considering
vacancies or holes in different orbitals rather than considering the large number of electrons. For
example, we may consider oxygen atom with the configuration 1s2 2s2 2p4 as two holes. The terms
derived in this way for p4 configuration are the same as for carbon with p2 configuration. The
terms are 1S, 1D and 3P. However, oxygen has more than half filled subshell and hence the order of
energy of 3P state as per the rules will be different than that for carbon. Therefore, the energy of 3P
states for oxygen are 3P2 > 3P1 > 3P0. Thus for oxygen 3P2 is the ground state. Similarly, by
considering holes, the terms for pair of atoms with pn and p6 – n arrangement and for dn and d10 – n
arrangement are indentical. Different terms for s, p and d configurations, are given in Table 4.4.
Table 4.4. Ground state and other terms for p and d configuration
Electronic Ground state Other terms
configuration term
s1 2S —
s2 1S —

p1, p5 2P

p2, p4 3P 1S, 1D

p3 4S 2D, 2P

p6 1S

d1, d9 2D

d2, d8 3F 3P, 1G, 1D, 1S

d3, d7 4F 4P, 2H, 2G, 2F, 2D, 2P

d4, d6 5D 3H, 3G, 3F, 3D, 3P, 1I, 1G, 1F, 1D, 1S

d5 6S 4G, 4F, 4D 4P, 2I, 2H, 2G, 2D, 2P, 2P, 2S

d10 1S

Calculation of Number of Microstates


The different ways in which the electrons can occupy the orbitals specified by the configuration
are called the microstates.

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 99

These microstates differ from one another slightly in energy. The number of microstates may
be calculated from the number of orbitals and the number of electrons using the formula :

 n n!
  =
r  r ! (n  r )!
where n is twice the number of orbitals and r is the number of electrons. n! and r! are factorial
n and factorial r respectively.
For a p2 configuration, there are three orbitals, so n = 6 and r = 2.
 n 6! 6  5  4  3  2 1
 No. of microstates,   =  = 15 microstates
r
  2! (6  2)! 2  1 4  3  2  1
Similarly, for a p3 configuration,
n = 6, r = 3
Using the above relation
 n 6! 6  5  4  3  2 1
 No. of microstates,   =  = 20 microstates
r  3! 3! 3  2  1  3  2  1
For a d2 configuration, there are five orbitals so n = 10 and r = 2.
 10  10! 10  9  8  7  6  5  4  3  2  1
 No. of microstate   =  = 45 microstates
2  2!8! 2  1  8  7  6  5  4  3  2  1
Using the above formula, the number of microstates for all the electronic arrangements p1 to
p and d1 to d10 can be calculated. These are given in Table 4.5.
6

Table 4.5. Number of microstates for various electron arrangements


Electronic No. of micro Electronic No. of microstates
arrangement states arrangement
p1 6 d1 10
p2 15 d2 45
p3 20 d3 120
p4 15 d4 210
p5 6 d5 252
p6 1 d6 210
d7 120
d8 45
d9 10
d10 1

4.5. ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES


The spectra which are obtained when electrons are promoted from one energy level (ground
state) to a higher energy level (excited state) are called electronic transitions. These are of high
energy and are always accompanied by lower energy vibrational and rotational transitions. The
vibrational and rotational energy levels are so close in energy that these cannot be resolved into
separate absorption bands and they cause considerable broadening of electronic absorption peaks in
d – d spectra. The band widths are usually of the order of 1000 to 3000 cm–1. The rules governing
these transitions are called selection rules. If the transition of electrons takes place according to a
set criteria, it is an allowed transition. If not, it is called a forbidden transition.

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
100 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

Selection Rules
The main selection rules for electronic spectra are :
1. Transitions in which there is change in the number of unpaired electrons in going from a
lower to a higher energy state are referred to as spin or multiplicity forbidden. This means that
transitions to only those excited states are to considered which have the same spin multiplicity as
the ground state. This is also known as S = 0 rule.
For example, for a d2 configuration, we observe transitions from 3F (ground state) to 3P (excited
state) because both 3F and 3P terms have same spin multiplicity 3. The transitions in which S  0(e.g.
S = ± 1) are forbidden or very very weak.
2. For molecules having a centre of symmetry, transitions which do not involve a change in
the subsidiary quantum number (l = 0) are forbidden. These forbidden transitions are called
Laporte forbidden transitions.
We can say that the transitions which involve a change in the subsidiary quantum number i.e.
l = ± 1 are Laporte allowed transitions and have a high absorbance. This rule suggests that
transitions from one d-level to another d-level (i.e. d–d transitions) in transition metal complexes are
not allowed (Laporte forbidden transitions) because l = 0.
This would suggest that transition metal complexes should not give d–d transitions and should
not give colours. But, actually it is not so. The transition do take place with the help of slight
relaxation in Laporte rule as explained below :
(i) If the transition metal complex ion does not have perfect octahedral structure, but is slightly
distorted so that the centre of symmetry is destroyed, then mixing of d and p-orbitals of the metal
ion may occur. In such a case, the transitions are no more pure d-d transitions but they occur between
d-levels with varying amounts of p-character. The intensity of such transitions is very weak in the
range  = 20 to 50. Thus, octahedral complexes in which all the ligands are not same such as
[Co(NH3)5 Cl]2+ have irregular octahedral structure and do not possess a centre of symmetry. d–d
transitions with varying amounts of p-character take place giving this compound a colour.
The tetrahedral complexes such as [MnCl4]2–, [MnBr4]2– etc. also do not possess a centre of
symmetry because a tetrahedron shape never possesses a centre of symmetry. Thus, intense transitions
are observed in these complexes which result in their deep colours. However, mixing of d and p
orbitals does not occur in perfectly octahedral complexes, which have a centre of symmetry such as
[Co(NH3)6]3+.
(ii) A complex which has a perfect octahedral structure can also exhibit absorption spectrum
because the bonds in the transition metal complexes are not rigid but undergo vibrations that may
temporarily change the centre of symmetry. These vibrations continue all the time and at any
particular time some ligands may spend an appreciable amount of time out of the centro symmetric
equilibrium position. As a result, the molecule may possess distorted octahedral symmetry so that
small amount of mixing of d and p-orbitals occurs and therefore, low intensity ( = 5 to 25) spectra
are observed. These transitions are called vibronically allowed transitions and the effect is called
vibronic coupling. For example, in [Mn(H2O)6]2+ complexes, all transitions are spin multiplicity
forbidden and Laporte forbidden. But the complex ion is pale pink in colour. This is explained by
vibronic coupling which results in very low intensity transitions.
In short Laporte allowed transitions are very intense while Laporte forbidden transitions vary
from weak intensity, if the complex is non centro symmetric to very weak if it is centro symmetric.

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 101

4.6. SPLITTING OF RUSSEL SAUNDERS STATES IN OCTAHEDRAL


AND TETRAHEDRAL CRYSTAL FIELDS
To understand the nature of electronic transitions in complexes of transition metals, we need
to know how the splitting of electronic energy levels and spectroscopic terms occurs in s, p, d and
f-orbitals. The following points may be noted.
(i) An s-orbital is spherically symmetrical and is not affected by an octahedral (or any other)
field. Hence no splitting is involved here.
(ii) The p-orbitals are directional but they have same type of orientation. These are affected by
an octahedral field but to equal extent. Therefore, their energy levels remain equal and no
splitting occurs.
(iii) The five d-orbitals are split by an octahedral field into two levels t2g (dxy, dyz, dzx) and eg
( d x2  y 2 , d z 2 ) having different energies. The difference between these two levels is 10Dq
(or 0). The t2g level is triply degenerate and is 4Dq below the bary centre, while eg level
is doubly degenerate and is 6Dq above the bary centre. For a d1 configuration, ground state
is a 2D state and the t2g and eg levels correspond to T2g and Eg spectroscopic states as shown
in Fig. 4.3 (a).
(iv) There are seven f-orbitals and these split by an octahedral field into three levels. For an f 1
arrangement, the ground state is a 3F state and is split into a triply degenerate T1g state which
is 6Dq below the vary centre, a triply degenerate T2g level which is 2Dq above the bary centre
and a single A2g state which is 12Dq above the bary centre as shown in Fig. 4.3 (b).

A2g

12Dq
Increasing Energy

T2g
Eg
2Dq
F
6Dq
D
6Dq
4Dq
T 2g T1g

(a ) (b)
Fig. 4.3. Splitting of spectroscopic terms arsing from
(a) d electronic arrangement and (b) f 1 electronic arrangement
1

We can summarise that in an octahedral field,


S and P states do not split
D states split into two states, Eg and T2g
F states split into three states, A2g, T2g and T1g
These states split by the external field are called Mulliken
symbols. These symbols are used in interpreting electronic spectra of
transition metal complexes.

Robert S. Mulliken

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
102 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

If may be noted that common Mulliken symbols are used in the octahedral and tetrahedral field
these are distinguished by introducing the symmetry symbol ‘g’ in octahedral field (Table 4.6)
Table 4.6. Correlation of Spectroscopic terms into Mulliken symbol
Spectroscopic Mulliken Symbol
Term Octahedral field Tetrahedral field
S A1g A1
P T 1g T1
D Eg + T2g E + T2
F A2g + T1g + T2g A2 + T1 + T2
G A1g + Eg + T1g + T2g A1 + E + T1 + T2
We can obtain Mulliken symbols if we know the spectroscopic terms S, P, D, F, etc. It may be
recalled that
(i) The term S stands for resultant angular momentum L, when L = 0. The number of
components of L is 2L + 1. When L = 0, this is called one component term and is represented
by A.
(ii) The term P means L = 1 which has 3 components (2L + 1). It is triply degenerate and is
represented by T.
(iii) The term D means L = 2 which has 5 components (2L + 1). This is constituted of doubly
degenerate E and a triply degenerate T terms.
(iv) The term G means L = 3 which has 7 components (2L + 1). This is constituted of one singly
degenerate A, a doubly degenerate E and two triply degenerate T1 and T2 terms.
We observe from the Table 4.6, that the singly degenerate term is sometimes represented by
A1 and sometimes by A2. Similarly triply degenerate terms are represented by T1 or T2. The numbers
1 and 2 define symmetry to Mulliken symbols and are derived from group theory.

4.7. SPECTROCHEMICAL SERIES


The arrangement of ligands in the increasing order of ligand field splitting energy () is called
spectrochemical series. The spectrochemical series in the decreasing order of ligand field splitting
is given below :
Increasing CFSE
I– < Br– < Cl– < SCN– < F– < OH– < acetate < Ox2– < H2O < NCS– < glycine < py  NH3
Weak field < en < dipy  o–phen < NO2– < CN– < CO
(small ) Strong field
(large )
A more compact form of the series involving most common ligands is :
Halides < C2O42– < H2O < NH3 < en < NO2– < CN– < CO
Ligands are commonly classified by their donor and acceptor capabilities. The ligands like
ammonia are  donors only, with no orbitals of appropriate symmetry for -bonding. The ligand field
splitting () depends on the degree of overlap. Ethylenediamine has a stronger effect than ammonia
among these ligands generating a larger .
The halide ions ligand field strengths are in the order :
F– > Cl– > Br– > I–
The small ligands can cause greater crystal field splitting because they can approach the metal
ion closely. For example, F– ion produces more than large Cl– ion and Br– ion.

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 103

With ligands having vacant * or d-orbitals, there is possibility of -back bonding with the
ligands. Such ligands are called -acceptors. This interaction to bonding scheme increases . The
ligands which can do this effectively are CN–, CO, etc. With -donor strength, ligands can be arranged
in terms of their donor atoms as :
halogen < oxygen < nitrogen < carbon
The metal ion also influences although not to the extent of ligands the magnitude of 0 through
the overlap and energy match criteria. The following metal ion spectrochemical series is observed.
Mn2+ < Ni2+ < Co2+ < Fe2+ < Fe3+ < Cr3+ < Co3+ < Mn4+ < Mo3+ < Pd4+ < Ir3+ < Re4+ < Pt4+
The crystal field splitting is influenced by the oxidation state of transition metal ion. Higher
the oxidation state of metal ion greater is the crystal field splitting.

4.8. SPECTRA OF TRANSITION METAL COMPLEXES


1. Spectra of d1 and d9 ions
(a) Octahedral complexes of metal ions with d1 and d9 configurations: In a free gaseous metal
ion, the five d-orbitals are degenerate. We do not expect electronic transition. However, when this ion
is surrounded by ligands the electrostatic field of the ligands splits the d-orbital into two groups, t2g
and e g. The simplest example of a d1 complex is Ti (III) to octahedral complexes such as
[Ti (H2O)6]3+. The splitting of d-orbitals is shown in Fig. 4.4 (a). In the ground state the single electron
occupies the lower t2g level and only one transition from t2g  eg is possible. Therefore spectrum
of [Ti(H2O)6]3+ shows only one band with a peak at 20300 cm–1 as shown in Fig. 4.4 (b). Wavelengths
corresponding to green and yellow light are absorbed from the white light while the blue and red portions
of the light are emitted. Therefore, Ti solution of complex [Ti (H2O)6]3+ looks purple.
Wavelength (Å)
3000 4000 5000 7000
eg 10

0.6 0 or 6 Dq
Molar absorbance

Average energy
Energy

5
level

0.4 0 or 4 Dq

Metal ion in t2g


spherical field 0
Metal ion in 30000 20000 10000
–1
(a) octahedral field Frequency (cm )
(b)
Fig. 4.4 (a) Splitting of energy levels for d1 configuration in an octahedral field and (b) visible
spectrum of [Ti (H2O)6]3+ complex ion.
We observe that the intensity of the absorption band is very weak ( = 5–10). This is because
it is a forbidden transition. The transitions from one centro symmetric d-orbital to another centro
symmetric d-orbital are forbidden. The molar absorbance value of such forbidden transitions are of
the order of  = 1 to 10 whereas allowed transitions have  values of about 10,000.
The magnitude of the splitting (0) depends upon the nature of the ligands. This affects the
energy of the transition and the frequency of maximum absorption vary in the spectra of these
complexes. For example, [TiCl6]3– absorbs at 13,000 cm–1, [TiF6]3– absorbs at 18900 cm–1 and
[Ti(H2O)6]3+ absorbs at 20300 cm–1, while [Ti(CN)6]3– absorbs 22300 cm–1. Consequently these
complexes show different colours.

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
104 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

The ground state terms for a free ion with d1 configuration is 2D and it is shown on the left
(Fig. 4.5). Under the influence of a ligand field, this splits into two states which are described by
Mulliken symbols 2Eg and 2T2g. The lower T2g state corresponds to the single d-electron occupying
one of the T2g orbitals and 2Eg state corresponds to the electron occupying one of the Eg orbitals.
The two states 2Eg and 2T2g are separated more widely as the strength of the ligand field increases.
2
Eg

6 Dq
Energy 2 Bary centre
D

4 Dq

2
T2g

Ligand field strength (Dq)


Fig. 4.5 Splitting of d-levels for d1 case in
octahedral field
Octahedral complexes of ions with d9 configuration. Spectra of complexes such as
[Cu(H2O)6]2+ can be explained on the similar lines as the Ti3+ octahedral complexes with a d1
arrangement. In the d1 complex there is a single electron in the lower T2g level while in the d9
complex, there is a single hole in the upper Eg level. Thus, the transition in the d1 case corresponds
to the promotion of an electron from the T2g to Eg level, whereas the transition in the d9 case
corresponds to the promotion of an electron as the transfer of a hole from Eg to T2g. That is why
the energy level diagram for d9 is the inverse of that for a d1 configuration (Fig. 4.6). In Fig. 4.6,
2E has been shown at lower level and 2T at a higher level.
g 2g
2
T2g

4 Dq
Energy

2
D Bary centre

6 Dq

2
Eg

Ligand field strength (0/Dq)

Fig. 4.6. Splitting of energy levels for d9 complex in octahedral field

4.9. ORGEL ENERGY LEVEL DIAGRAMS


The plots of variation of energy level of spectroscopic states of different symmetry as a
function of field strength Dq are called Orgel diagram. This concept was developed of Leslie Orgel.
The energy level diagram for d1 and d9 in octahedral field (Oh) are shown in Fig. 4.7. This figure
is the combination of Fig. 4.5 and 4.6.

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 105

2
Eg 1 9 2
T2g
d (Oh) d (Oh)

6 Dq
0 Bary
Energy

2
D centre
4 Dq

2 2
T2g Eg

O
Increasing (Dq) Increasing (Dq) Leslie Orgel
Fig. 4.7 Splitting of energy levels for d1 and d9 configurations in an octahedral field (Oh)

Tetrahedral complexes of metal ions with d1 and d9 configurations


We have learnt earlier that in tetrahedral field, d-orbitals split into two e orbitals of lower
energy and three t2 orbitals of higher energy.
In the case of tetrahedral ligand field, the energy level diagram is inverse of that of octahedral
field. The main difference between tetrahedral field and octahedral field is that the splitting is only
4/9 as that of octahedral field (t= 4/9 o).
Similarly, the tetrahedral complex of d9 configuration have energy levels inverse of d1
configuration. So, the energy level diagram for d9 configurations will also be inverse of that of
octahedral field. The splitting of energy levels of d1 and d9configurations in tetrahedral field (Td)
are shown in Fig. 4.8. The inverse relation between tetrahedral complexes and octahedral complexes
with d1 configuration and also with d9 configuration can be understood from Fig. 4.8. Similarly,
inverse relation between tetrahedral complexes with d1 and d9 configuration can also be understood
from this figure.
2
E 9 1 2
T
d (Td) d (Td)
Energy

2
D

2 2
T E

O
Increasing (Dq) Increasing (Dq)

Fig. 4.8. Splitting of energy levels for d1 and d9 configurations in a tetrahedral field (Td)
To summarise, we can say
d1 (Td) is inverse of d9 (Td) as well as d1 (Oh)
d9 (Td) is inverse of d1 (Td) as well as d9 (Oh)
We can check that the value of L is the same in the case of d1 and d6 configurations, but the
spin multiplicities are different

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
106 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

+2 +1 0 –1 –2
1 1
d L = 2, spin multiplicity (2S+1) = (2× + 1) = 2
2
6
d L = 2, spin multiplicity (2S+1) = (2 × 2 +1) = 5

Thus the term symbols for d1 and d2 configurations are 2D and 5D respectively. The state D
splits into doubly degenerated term E and triply degenerate tem T in octahedral as well as tetrahedral
fields. Consequently, only a single d-d transition can occur. Thus, we come to know that electronic
transitions will be similar for d9 (2D) and d4 (5D). In other words, transitions in metal ions differing
by five d-electrons in their configurations give similar transitions in octahedral and tetrahedral fields.
From the Orgel diagram (Fig. 4.9) it is apparent that d1, d4, d6 and d9 ions should also give
only one d-d absorption band. Splitting of the states as a function of o for octahedral complexes
with d1 and d6 electron configurations and tetrahedral complexes with d4 and d9 electron
configurations are described on the left handside. The spectra of these complexes contain only one
band arising from d-d transitions and is assigned as T2g  Eg.
The right hand side of the Orgel diagram applies to octahedral complexes with d4 and d9
electron configurations and tetrahedral complexes with d1 and d6 electron configurations. The
spectra of these complexes contain only one band arising from single d-d transitions and is assigned
as E  T2. For tetrahedral complexes we drop the subscripts because a tetrahedron does not
have centre of symmetry.

Eg 1 6 4 9 T2g
d ,d (Oh) d ,d (Oh)
4 9 1 6
d ,d (Td) d ,d (Td)

T2g Eg
O
Increasing (Dq) Increasing (Dq)

Fig. 4.9. Orgel diagram of d1, d4, d6 and d9 complexes in octahedral and tetrahedral fields
From the Orgel diagram (Fig. 4.9), we conclude that electronic transitions in:
d1 (Oh) = d6(Oh) but inverse of d9 (Oh) = d4 (Oh) and
d1(Td) = d6 (Td) but inverse of d9(Td) = d4 (Td)

Spectra of d2 and d8 ions

(a) d2 Octahedral field


In the ground state for a d2 configuration, the two electrons occupy different orbitals. In an
octahedral field, the d-orbitals are split into three t2g orbitals of lower energy and two eg orbitals of
higher energy. The two d-electrons occupy t2g orbitals because of their lower energy. The inter electron
repulsions would split the levels giving the spectroscopic terms for d2 electron configuration as
1S, 3P, 1D, 3F and 1G

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 107

3F
is the ground state with lowest energy and 3P, 1G, 1D and 1S are excited states in accordance
with Hund’s rule. The transitions from the level 3F are allowed to another triplet state i.e. 3P. The
transitions from 3F to 1S, 1D and 1G states are spin forbidden and are not observed. p-orbitals are
not split in an octahedral field and so P states are not split but are transformed into a3 T1g state while
the f-orbitals are split into three levels and so 3F state splits into 3A2g + 3Tlg + 3T2g. The energy
level diagram for these is shown in Fig. 4.10 (a).
3
A2g (F)
3 3
T1g (F)  T1g (P)
3 3
T1g (F)  A2g
3
T1g (P) 10

Molar absorbance
3
3
T2g (F)
3 3
P T1g (F)  T2g
Energy

3
F 5

3 40000 30000 20000 10000


T1g (F)
–1
Ligand field strength Frequency cm
(a) (b)

Fig. 4.10 (a) Transitions for V3+ (d2) ion and (b) Absorption spectrum of a d2 complex [V(H2 O)6]3+.
We expect three peaks corresponding to three transitions as shown in Fig. 4.10 (a). The three
transitions are from the ground state 3T1g (F) to 3T2g 3T1g (P) and 3A2g respectively. The spectrum
of [V(H2O)6]3+ is shown in Fig. 4.10 (b) which shows only two peaks. The peak at ~17,000 cm–1
is assigned to 3Tlg (F)  3T2g (F) and the peak at  24,000cm–1 is due to both 3T1g (F) 
3T (P) and 3T (F)  3A
1g 1g 2g transitions.
2+
Thus, for [V(H2O)6] , the bands are assigned as:
3T (F)  3T2g (F) 17,000 cm–1
1g
3T (F)  3A2g (F) 24,000 cm–1
1g
The energies corresponding to these two transitions lie very close to each other and therefore,
these two transitions are not resolved into two separate peaks.
However, with strong field ligands like NH3, we get three bonds which may be assigned as:
3T (F)  3T2g (F) 17,200 cm–1
1g
3T (F)  3T 1g (P) 25,600 cm–1
1g
3T (F)  3A2g (P) 36,000 cm–1
1g

(b) d2 Tetrahedral field


A few tetrahedral complexes also exhibit two bands in the range of 9000 cm–1 corresponding
to 3A2 (F)  3T1(F) and 15000 cm–1 corresponding to 3A2 (F)  3T1 (P) transitions.
3A (F)  3T1 (F) 9,000 cm–1
2
3A (F)  3T1 (P) 15,000 cm–1
2

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
108 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

The transition 3A2 (F)  3T2 (F) is of very low energy and does not fall in the visible
region and hence is not observed in the electronic spectrum of d2 (Td).

(c) d8 Octahedral
The complexes of metal with d8 configuration can be treated similar to d2 octahedral
complexes. There are two holes in the eg level and therefore, promoting one electron is equivalent
to transferring a hole from eg to t2g level. This is inverse of d2 case and is shown in Fig. 4.11. As
explained earlier 3P state is not split and is not inverted but the 3F state is split into three states and
is inverted. Hence the ground state term for Ni2+ is 3A2g. It may be noted that in both d2 and d8
configuration, the 3F state is the lowest energy state. Three spin allowed transitions are observed
in spectra of [Ni (H2O6]2+, [Ni (NH3)6]2+, etc. The transitions correspond to the following.
3A 3
2g  T2g (F)
3T 3
2g  A1g (F)
3TA 3
2g  A1g (P)
3
3 T1g (P)
P
3
T1g (F)
Energy

3
3
F T2g

3
A2g
Ligand field strength
Fig. 4.11 Energy level diagram for d8 ion.
It may be noted that d2 octahedral energy level diagram is similar to the high spin d7
octahedral and d3 and d8 tetrahedral cases. The inverse diagram is similar for d3 and d8 octahedral
and d2 and d7 tetrahedral complexes.
Fig. 4.12 gives Orgel diagram for two electrons and two hole configuration 4.12. In this figure,
the two T1g states, one from P state and other from F state are slightly curved lines. This may be
attributed to mixing between the two T1g terms arising from the high energy P term and low energy
F term because of same symmetry possessed by them.
3
8 Energy 2 A2g (F)
3 d (Oh) d (Oh ) 3
T1g (P) 2
d (Td ) 3
8
d (Td) T1g (P)
P
3
T1g (F)
3 3
F T2g (F)

3
T2g (F)
3
T1g (F)

3
A2g (F)
O Dq
Increasing ligand field Increasing ligand field
Fig. 4.12. Orgel diagram for two electron (d2) and two hole (d8) configuration

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 109

ELECTRONIC SPECTRA OF SOME WELL-KNOWN COMPLEXES


1. Cr (III) octahedral complexes : d3 (Oh)
In the octahedral complex such as Cr(H2O)6]3+ Cr (III) (d3) has electron configuration : t2g3.
The d3 arrangement gives rise to two states 4F and 4P. In an octahedral field 4F state splits into 4A2g
(F), 4T2g (F) and 4T1g (F) states while 4P state does not split out transforms into a 4T1g (P).
Increasing order of energies of different states is:
4T (F) < 4T (F) < 4T (F) < 4T (P)
2g 2g 1g 1g
4
F1g(P)
4
P
4
T1g(F)

4
F
4
T2g(F)

4
A2g

Ligand strength
Fig. 4.13 Energy level diagram for a d3 ion.
The Orgel energy level diagram is shown in Fig. 4.13. The spectra of Cr (III) complexes would
be expected to show three absorption peaks corresponding to the following transitions:
For [Cr(H2O)6]3+
4A (F)  4T2g (F) 17,400 cm–1
2g

4A (F)  4T1g (F) 24,500 cm–1


2g

4A (F)  4T1g (P) 38,600 cm–1


2g
Most of the Cr (III) complexes show two well-defined absorption peaks in the visible region
while some complexes show the third band though it is often overlapped by a very intense charge
transfer band. Transitions between ground term and higher states and corresponding bands (cm–1)
for some Cr (III) complexes are given below in Table 4.7.
Table 4.7 Electronic transitions (in cm–1) of some Cr3+ (Oh) complexes.

Complex

Transition [CrF6]3– [Cr(H2O)6]3+ [Cr(ox)3]3– [Cr(en)3]3+ [Cr(CN)6]3–


Green Violet Red-violet Yellow Yellow
4A 4
2g  T2g (F) 14,900 17,400 17,500 21,900 26,700

4A 4
2g  T1g (F) 22,700 24,700 23,000 28,500 32,200

4A 4
2g  T1g (P) 34,400 38,600 –– –– ––

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
110 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

In d3 tetrahedral complexes, the following transitions ocur:


(i) 4T1 (F)  4T2 (F) (ii) 4T1 (F)  4A2 (F) (iii) 4T1 (F)  4T1 (P)

2. Manganese (II) octahedral complex ions: d5 (Oh)


In high spin octahedral complexes such as [MnF6]4–, [Mn(H2O)6]2+, Mn(II) has t2g3, eg2
electronic configuration. The ground state term is 6S and there are five unpaired electrons with
parallel spins. Any electronic transition within d level must involve a reversal of spins and therefore
these d––d transitions are spin forbidden transitions and are very weak. That is why Mn(II)
compounds have pale pink colour.

0.03 4
A1g
Molar absorbance

4 4G
Eg
4
0.02 4 T2g (4D)
T1g (4G)
4
T2g (4G) 4
Eg (4D)
0.01

20000 25000 30000


–1
Frequency cm
Fig. 4.14. Electronic spectrum of [Mn (H2O)6]2+
The spectrum of [Mn(H2O)6]2+ is shown in Fig. 4.14. It has the following features:
(i) The molar absorption coefficients,  is about 0.02 – 0.03 l mol–l cm–1 as compared with
5–10 l mol–1 cm–1 for spin allowed transitions. Thus the bands are very weak.
(ii) A large number of bands is obtained.
(iii) Some of the bands are sharp while others are broad.
The spectrum can be explained as follows:
(a) The ground state term of Mn(II) is 6S. This state does not split but transforms to the A1g
state in a weak octahedral field (drawn along the horizontal axis). This is the only sextuplet state
and any alteration which may occur on electron excitation results in pairing of two or four spins,
thus resulting in doublet or quartet states. Therefore, all excited states will have different spin
4
50000 T2g
4
T1g
4
F 4
40000 A2g
4
4 T1g
Energy

D 4
30000 Eg
4
4 4 T2g
P E g 4A
4 1g
G 4
20000 T2g
4
T1g

10000
6
6 A1g
S
500 1000
Ligand field strength
Fig. 4.15. Orgel energy level diagram for Mn2+ (d5) octahedral

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 111

multiplicity compared to the ground state and therefore, transition to these excited states are spin
multiplicity forbidden. However, due to weak spin orbital interactions, these types of transitions
are not totally forbidden but give rise to weak absorption bands.
(b) For the ground state term 6S, there are 11 excited states (4G, 4F, 4D, 4P, 2I, 2H, 2G, 2F,
2D, 2P, 2S. Out of these 11 excited states only four quarters, 4G, 4F, 4D and 4F involve the reversal

of only one spin. Rest of the seven states are doublets and are doubly spin forbidden and are unlikely
to be observed. In octahedral field, these four states split into ten states and therefore, upto ten weak
absorption bands may be observed as shown in Fig. 4.15.
(c) Calculations shows that width of the peaks for d-d transitions vary directly as the slope
of the higher energy state relative to the slope of the ground state in the Orgel diagram. Fig. 4.15
shows that the ground state 6S does not split but transforms to 6A1g state which is drawn along the
horizontal line. The 4Eg(G), 4A1g (G), 4Eg(D) and 4A2g(F) terms are also horizontal lines. So, their
energies are independent of the crystal fields. Since the slope of the ground state terms 6A1g is zero
and the slopes of 4Eg(G), 4A1g(G), 4Eg(D) and 4A2g (F) terms are also zero, transitions from the
ground state to these four states should give sharp peaks. Similarly, the peaks due to transitions to
4T (G) and 4T (G) will give broad peaks. These bands are listed as under.
1g 2g
6A  4T 1g 18900 cm–1
1g
6A  4T2g (G) 23100 cm–1
1g
6A  4E g 
1g 24970 and 25300 cm–1
6A
1g
 4A1g 
6A  4T2g (D) 28000 cm–1
1g
6A  4Eg (D) 29700 cm–1
1g
For tetrahedral complexes of d5 electronic configuration, the same diagram is applicable.
3. Cobalt (III) octahedral complex ions : d7 (Oh)
In octahedral field of weak ligands, Co(II) has the electronic configuration as : t2g5 eg2. Thus
it has three unpaired electrons. The ground state term is 4F which is transformed to 4T1g (F), 4T2g
and 4A2g. The other quartet states is 4F which does not split but transforms into 4T1g(P) state is an
octahedral field. The energy level diagram is shown in Fig. 4.16.
4
A2g
4
T1g(P)
4
P
Energy

4
T2g
4
F

4
T1g(F)

Ligand field strength

Fig. 4.16 Energy level diagram for Co (II) octahedral complexes.


The figure shows that an octahedrally coordinated Co (II) ion should exhibit the following
three spin allowed d-d transitions:

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
112 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

Molar absorbance
4

25000 20000 15000 10000 5000


–1
Frequency (cm )

Fig. 4.17 The absorption spectrum of octahedral complex of [Co (H2O)6]2+


4T (F)  4T2g (F) 8700 cm–1 Near IR
1g
4T (F)  4A2g (F) 16,000 cm–1
1g
4T (F)  4T 1g (P) 19,400 cm–1
1g
The absorption spectrum of [Co(H2O)6]2+ (Fig 4.17) is weak and occurs in the blue part of
the visible region and therefore accounts for the pale pink colour of the [Co(H2O)6]2+ ion.
The absorption band at 8700 cm–1 which falls in the near infra red region is assigned to 4T1g
(F)  4T2g(F). A multiple absorption band appears at about 20,000 cm–1. It has three peaks
at 16,000, 19400 and 21600 cm –1 . The main band at 19,400 cm –1 is assigned to 4T 1g
(F)  4T1g(P) and the shoulder at 16000 cm–1 to 4T1g(F)  4T2g(F). It is a two electron
process and is therefore very weak as compared to the 4T1g(F)  4T1g(P) transition because
two electron transitions lie very close to 4T1g(F)  4A2g transition. Therefore, the transitions
are not observed as separate peak.
These transitions are close together because of cross over point between 4A2g and 4T1g(P).
The extra shoulder is due to spin orbit coupling in 4T1g (P) state.

Co(II) Tetrahedral complex ions


Co2+ in the tetrahedral complex, [CoCl4]2– has d7 configuration. In this complex the electron
configuration is e4t23. This energy level diagram is same as given for Cr (III) octahedral complex
ions (Fig. 4.16). The absorption spectrum of [CoCl4]2– is shown in Fig. 4.18. The absorption occurs
in the red part of the spectrum and is very intense and this is responsible for the deep blue colour
of Co(II) tetrahedral complexes. This absorption band is assigned to the transition:
4A
(F)  4T1 (P) 2
The other transitions caused by spin-orbit coupling are
4A (F)  4T2 (F) and
2

4A (F)  4T1 (F)


2
However, the only band which appears in visible region is at 15,000 cm–1 corresponding to
4A (F)  4T (P) occurring in the red part of the spectrum. The other two transitions (i) 4A
2 1 2
 4T2 fall in the infrared region (33,00 cm–1) and (ii) 4A2  4T1 (F) appears in the near
infrared region (58,00 cm–1). The various transitions can be listed as under:

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 113

4A (F)  4T2 (F) 33,00 cm–1 (infrared region)


2

4A (F)  4T1 (F) 58,000 cm–1 (near infrared)


2

4A (F)  4T1 (P) 15,000 cm–1 (visible region)


2

600

400
Molar absorbance

200

25000 20000 15000 10000 5000


–1
Frequency (cm )

Fig. 4.18 Absorption spectrum of [CoCl4]2– ion.

4. Nickel (II) octahedral complex ions: d8(Oh)


The spectra of [Ni(H2O)6]2+ can be understood by considering the energy level diagram
(Fig. 4.19). Three spin allowed transitions are expected and these are assigned to the following
transitions:
3A (F)  3T2g (F) 8500 cm–1
2g

3A (F)  3T1g (F) 15,400 cm–1


2g

3A
(F)  3T1g (P) 26,000 cm–1
2g
Similarly, these band in [Ni(NH3)6]2+ complex ocur at 10800, 17500 and 28200 cm –1
respectively. The bands are quite weak as expected.

10
Molar absorbance

3 3
5 A2g  T1g(P)

3 3
3 3 A2g  T2g
A2g  T1g(F)

30000 20000 10000


–1
Frequency (cm )

Fig. 4.19. Absorption spectrum of [Ni (H2O)6]2+ ion.

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
114 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

Limitations of Orgel Energy Level Diagrams


1. The Orgel energy level diagrams consider only the energy levels obtained by splitting the
energy terms when the metal ion is subjected to weak octahedral field or tetrahedral field. In other
words, Orgel energy level diagrams consider only weak field (or high spin) cases.
2. The Orgel energy level diagrams consider spin allowed transitions in which the ground and
excited states are of same multiplicities. Orgel diagrams do not consider the excited states of
multiplicities different from those of ground state.

SOLVED CONCEPTUAL PROBLEMS


Example 1. What is meant by ground state term symbol? How is it calculated? Explain
with an example.
Solution. Term symbol corresponding to a state with maximum S and L is called ground state
term symbol. The following steps are involved to determine the ground state term symbol.
1. Start with the most stable electron configuration. Full shells and subshells do not contribute
to the overall angular momentum, so they are discarded.
 If all shells and subshells are full then the term symbol is 1S0.
2. Distribute the electrons in the available orbitals, following the Pauli exclusion principle.
First, we fill the orbitals with highest ml value with one electron each, and assign a maximal ms to
them (i.e. + 1/2). Once all orbitals in a subshell have one electron, add a second one (following the
same order), assigning ms= –1/2 to them.
3. The overall S is calculated by adding the ms values for each electron. That is the same as
multiplying 1/2 times the number of unpaired electrons. The overall L is calculated by adding the
ml values for each electron (so if there are two electrons in the same orbital, then we add twice that
orbital’s ml).
4. Calculate J as:
 if less than half of the subshell is occupied, take the minimum value J = |L–S|;
 if more than half filled, take the maximum value J = L + S ;
 if the subshell is half filled then L wil be 0, so J = S.
As an example, in the case of fluorine, the electronic configuration is : 1s22s22p5.
1. Discard the full subshells and keep the 2p5 part. So we have five electrons to place in
subshell p (l =1).
2. There are three orbitals (ml = 1, 0, –1) that can hold up to 2(2l+1) = 6 electrons. The first
three electrons can make ms = 1/2 () but the Pauli exclusion principle forces the next two to have
ms= –1/2() because they go to already occupied orbitals.

ml
+1 0 –1
ms:

3. S = 1/2 + 1/2 + 1/2 –1/2 –1/2 = 1/2; and L = 1 + 0 –1 + 1 + 0 = 1, which is “P” in


spectroscopic notation.
4. As fluorine 2p subshell is more than half filled, J = L + S = 3/2. Its ground state term symbol
is then 2S+1LJ = 2P3/2.

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 115

Example 2. The [Ti (H2O)6]3+ complex absorbs at 5000Å. Calculate  0 for this absorption.
N 0hc
Solution. E = N0 hv =

For [Ti (H2O)6]3+
 = 5000Å = 5000 × 10–10 m, c = 3.0 × 108 ms–1, h = 6.626 × 10–34 Js
N0 = 6.023 × 1023. Substituting the values in the equation above
6.023  10 23  6.626  10 –34  3.0  108
E = =239 kJ mol–1
5000  10 –10
 0 for the complex = 239 kJ mol–1.
Example 3. Derive the term symbols for d10 configuration.
Solution. In a d10 configuration
2 1 0 –1 – 2
    
ML= 0 so L = 0 and it corresponds to ‘S’ state.
Ms= 0 and so S = 0 and therefore, multiplicity is 2S + 1 = 1
 Term symbol : 1S
It may be noted that for a closed configuration, the term symbol is always 1S.
Example 4. The tetrahedral complexes of Mn (II) are more intensely coloured than the
octahedral complexes of Mn (II). Explain.
Solution. Manganese (II) has d5 electronic configuration. Tetrahedral Mn (II) complexes are
yellow green. The d–d transitions in tetrahedral Mn (II) complexes are quite intense than octahedral
complexes. These d–d transitions are Laporte allowed because tetrahedral molecules do not possess
centre of symmetry. The transitions in Mn (II) d5 are also multiplicity allowed due to mixing of d-
and p-orbitals in tetrahedral geometry. Hence we observe intense coloured Mn (II) tetrahedral
complexes.
On the otherhand, in [Mn (H2O)6]2+ octahedral complexes, the transitions are both Laporte
forbidden (due to centre of symmetry) and multiplicity forbidden because ground term 6A1g is the
only term with multiplicity 6 and all other terms are of lower multiplicity. Therefore, the bands are
very weak.
Example 5. Identify the ground state terms from each set of terms:
(i) 1S, 3P, 1D, 3F, 1G
(ii) 1S, 3P, 1D
(iii) 1S, 2P, 2D, 3F, 1G
Solution. (i) 3F because although it has same multiplicity as 3P but it has higher value of L
(=3) and hence more stable.
(ii) 3P because it has highest multiplicity.
(iii) 3F because it has highest multiplicity.
Example 6. Calculate the number of microstates for:
(i) d1 (ii) p3 (iii) d4 configurations
Solution. (i) d1
Here n = 10, r = 1
Applying the formula to calculate number of microstates

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
116 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

n n! 10! 10!


No. of microstates  r  = r !(n – r)! = 1!(10 – 1)! =
  1!9!

10  9  8  7  6  5  4  3  2  1
= = 10
1 9  8  7  6  5  4  3  2  1
(ii) p3
n = 6, r=3
6! 6! 6  5  4  3  2  1
No. of microstates = 3!(6 – 3)! = = = 20
3!3! 3  2 1 3  2  1
(iii) d4
n = 10, r=4
10! 10! 10  9  8  7  6  5  4  3  2  1
No. of microstates = 4!(10 – 4)! = = = 210
4!6! 4  3  2 1 6  5  4  3  2 1
Example 7. Determine the term symbol for ground state of nitrogen.
Solution. The electronic configuration of nitrogen, N is 1s2 2s2 2p3. We consider only 2p
subshell because the inner orbitals are filled.
l + 1 0 –1
2p   
ML = +1 + 0 – 1 = 0 It corresponds to state S.
1 1 1 3
MS =    
2 2 2 2
23
 Spin multiplicity 2S + 1 = 1 = 4
2

Since ML = 0, J has only one value equal to MS i.e. J = 3 2

 Term symbol for N is 4 S 3 .


2

Example 8. Electronic transitions of d–d type in octahedral complexes should be


forbidden by the Laporte selection rule. Why are moderately strong spectra observed in
certain cases?
Solution. Electronic transitions of d–d type are Laporte forbidden only under the conditions
of centro symmetric octahedral complexes. However, in substituted octahedral complexes such as
[Co(NH3)5Cl]2+, some mixing of d and p-orbitals may occur. Therefore the transitions in these
complexes are no longer pure d-d in nature, rather mixed d and p type which are moderate in
intensity. Hence, non centrosymmetric octahedral complexes give strong d-d transitions and have
moderately strong spectra.
Example 9. Determine the term symbols for
(i) s1p1 (ii) d1s1 (iii) d7s1
Solution. (i) s1p1
 1 0 –1 0
p  s 

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 117

ML = + 1 + 0 = 1  State = P
1 1
MS = + =1 S=1
2 2
Spin multiplicity, = 2S + 1
= 2 × 1 + 1= 3
 Term symbol : 3P
(ii) d1s1
 2 1 0 – 1 – 2 0
 
ML = 2 + 0 = 2  State = D
1 1
MS = + =1 S=1
2 2
Spin multiplicity, = 2S + 1 = 2 × 1 + 1= 3
 Term symbol : 3D

(iii) d7s1
 2 1 0 – 1 – 2 0
     
ML = 4 + 2 + 0 – 1 – 2 + 0 = 3  State = F
1
MS = 4 × =2 S = 2
2
Spin multiplicity, 2S + 1 = 2 × 2 + 1 = 5
 Term symbol : 5F
Example 10. What terms arise from p1d1 configuration?
Solution.
 1 0 –1 2  1 0 – 1 – 2
p  
For a p1d1 configuration,
ML = +1 + 2 = 3  Term = F
The electrons may be paired, S = 0 or parallel, S = 1
Spin multiplicity 2S + 1 = 2 × 0 + 1 = 1 or 2 × 1 + 1 = 3
Terms 1F and 3F are possible corresponding to the two spin multiplicities
Example 11. Calculate the number of microstate for
(i) p4 and (ii) d4 configurations.
Solution. Microstates can be calculated using the formula :

 n n!
No. of microstates :   =
r  r ! (n  r )!
n = twice the no. of orbitals and r = the number of electrons.

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
118 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

(i) for p4
n = 6, r = 4, Substituting the values
6!
No. of microstates =
4! (6  4)!

6! 6  5  4  3  2 1
= 
4! 2! 4  3  2  1  2  1
= 15 microstates
(ii) for d4 configuration,
n = 10, r = 4, Substituting the values, we have
10! 10!
No. of microstates = 
4! (10  4)! 4! 6!

10  9  8  7  6  5  4  3  2  1
=
4  3  2 1 6  5  4  3  2 1
= 210 microstates
Example 12. What is vibronic coupling? Give one example of this phenomena.
Solution. The d-d transition in octahedral complexes are Laporte forbidden on symmetry
consideration. However an octahedral (Oh) complex may absorb light in the following manner.
The bonds in the transition metal complexes are not rigid but may undergo vibrations that may
temporarily change the symmetry. Some of the molecules may slightly be distorted from octahedral
symmetry at a given time. For example, octahedral complexes vibrate in a way in which the centre
of symmetry is temporarily lost. This phenomenon is called vibronic coupling. As a result, d-d
transitions having molar absorptivities in the range of approximately 10 to 50 L mol–1 cm–1 are
commonly observed. These are also responsible for the bright colour of many of these complexes.
For example, this phenomenon is observed in [Mn(H2O)6]2+. In this case, the transitions are both
multiplicity and Laporte forbidden. The complex is coloured. Had there been no vibronic coupling
it would have been colourless. These transitions are vibronically allowed and the effect is called
vibronic coupling.
Example 13. Calculate the term symbols for ground state of
(i) Cr (3d5 4s1) and (ii) Ni (3d8 4s2).
5
Solution. (i) Cr : 3d 4s 1

 2 1 0 –1 – 2 0
3d      4s 

ML = + 2 + 1 + 0 – 1 – 2 + 0 = 0  State = F
1
MS = + × 6 = 3, S =3
2
Multiplicity, 2S + 1 = 2 × 3 + 1 = 7
J = 3 (because L = 0)
 Term symbol for ground state = 7S3

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 119

(ii) Ni : 3d8 4s2


 2 1 0 –1 – 2 0
3d      
ML = + 4 + 2 + 0 – 1 – 2 + 0 = 3 State = F
1
MS = + ×2=1 S=1
2
Multiplicity, = 2 × 1 + 1 = 3
J =3+1=4
 Term symbol for ground state = 3F4
Example 14. Identify the ground state terms from each set of following giving reasons.
(a) 3F2, 3F3, 3F4 (b) 1S, 2P, 2D, 3F, 1G (c) 1S, 3P, 1D, 3F, 1G
3
Solution. (a) F2 is the ground state term. L and S values are same for all the three cases. The
ground term is determined by J. For less than half filled (d2 in the present case), the minimum value
of J gives the ground state.
(b) 3F is the ground state term because it has highest multiplicity
(c) 3F is the ground state term because it has higher value of L (= 3) but same multiplicity as
3P (L = 2).

Example 15. Derive states for d2 configuration.


Solution. For d2 configuration :
l1 = l2 = 2
L = (2 + 2), (2 + 2 –1), (2 + 2 –2) (2 + 2 –3), (2 + 2 –4)
=4 3 2 1 0
 States = G, F, D, P, S
Since there are two electrons so
S = 1, 0
or 2S + 1 = 3, 1
Hence term states for d2 configurations are:
3G, 3F, 3D, 3P, 3S, 1G, 1F, 1D, 1P, and 1S.

Example 16. Determine the ground terms for low spin and high spin d6 octahedral
configurations.
Solution. High spin :
 2 1 0 – 1 – 2
    

ML = + 2 + 2 + 1 + 0 – 1 – 2 = 2  State = D
1
MS = 4+ = 2
2
Spin multiplicity = 2 × 2 + 1 = 5
 Term symbol = 5D
Low spin :
  

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
120 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

ML = + 2 + 2 + 1 +1 + 0 + 0 = 6,  State = I
MS = 0  Multiplicity = 2 × 0 + 1 = 1
 Term = 1I
Example 17. Determine the possible values of J for the term obtained from a d 2
configuration.
Solution. For d2 configuration:
l1 = 2, l2 = 2
L = (2 + 2), (2 + 2 –1), (2 + 2 –2), (2 + 2 –3), (2 + 2 –4)
=4 3 2 1 0
 States = G, F, D, P, S

1 1 1 1
Since there are two electrons so, S = 1  2  2  , 0  2 – 2 
   
or Spin multiplicity S = (2S + 1) = 3, 1
Possible values of J are:
L = 4, S = 0, J = 4 1G

L = 3, S = 1, J, 4, 3 3F

L = 2, S = 0, J = 2 1D

L = 1, S = 1, J = 2, 1, 0 3P
L = 0, S = 0, J = 0 1S

Example 18. Explain the terms:


Term, Level
Solution. The combination of an S value and an L value is called a term and has a statistical
weight (i.e number of possible microstates) of (2S + 1) (2L + 1).
A combination of S, L and J is called a level. A given level has a statistical weight of (2J +
1), which is the number of possible microstates associated with this level in the corresponding term.
For example, for S = 1, L = 2, there are (2 × 1 + 1) (2 × 2 + 1) = 15 different microstates
corresponding to the 3D term, of which (2 × 3 + 1) = 7 belong to the 3D3 (J = 3) level. The sum of
(2J + 1) for all levels in the same term equals ( 2S + 1) (2L + 1). In this case, J can be 1, 2 or 3 so
3 + 5 + 7 = 15.
Example 19. Give the ground state term symbols for H(1s1) and He (1s2)
Solution. H (1s1)
Ground state term symbol is 2S1/2
H (1s2)
Ground state term symbol is 1S0
Example 20. Why do tetrahedral complexes of an element give much more intense d-d
spectra than its octahedral complexes?
Solution. Tetrahedral complexes do not have centre of symmetry and therefore, d-d transitions
in tetrahedral complexes are Laporte allowed. The Laporte allowed transitions are very intense.
Therefore, such transitions give intense bands in tetrahedral complexes. On the other hand,
octahedral complexes show only very weak transitions due to possibility of some mixing.
Example 21. Give the term symbols for
(a) He (1s2 2s1) in excited state
(b) B (1s22s22p1)

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 121

Solution. (a) He (1s2 2s1)


Term symbols 1S0, 3S1
(b) B ( 1s2 2s2 2p1)
Term symbols 2P1/2, 2P3/2
Example 22. Give the number of microstates in N (1s22s22p3). Give the distribution in
different term symbols in N.
6!
Solution. No. of microstates = = 20
3!3!
Distribution
2 D = 10
2P = 6
4S = 4

Total 20

EXERCISES
(Including Questions from Different University Papers)
Multiple Choice Questions (Choose the correct option)
1. Ground state term symbol for He (1s2) is
(a) 1S1/2 (b) 1S0
(c) 0S1/2 (d) none of these
2
2. Ground state term for d configuration is:
(a) 3F (b) 3P (c) 1G (d) 1S
3+
3. The colour of the complex ion, [Ti(H2O)6] is due to:
(a) presence of water molecules
(b) intermolecular vibrations
(c) excitation of electron from t2g to eg energy level
(d) excitation of electron from 3d to 4s energy level
4. The number of microstates for a p2 configuration is
(a) 10 (b) 20 (c) 18 (d) 15
5. For L = 0 and S = 1, full spectroscopic term is :
(a) 3D1 (b) 1S1 (c) 3S1 (d) 1P3
6. Which of the following electronic arrangement has maximum number of microstates?
(a) d 5 (b) d 3 (c) d 6 (d) d 9
5
7. Ground state term of d configuration is :
(a) 6S (b) 4F (c) 2D (d) 3P
8. For Laporte forbidden transitions
(a) l = 0 (b) S = 0 (c) l = –1 (d) l = ±1
9. Mulliken symbol for spectroscopic term P in octahedral field is
(a) A1g (b) T 1g (c) T 2g (d) Eg

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
122 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

10. The ground state for 2p3 is


(a) 4S3 (b) 3F4 (c) 4S
3/2 (d) 2P
1
11. The ground state term for p6 is same for
(a) d10 (b) d6 (c) p3 (d) d5
12. The lowest energy term for d2 ion is
(a) 3F (b) 1S (c) 3P (d) 4P
13. Which of the following corresponds to absorption peak of maximum wave number in
[Cr(H2O)6]3+ complex ion?
(a) 4A2g  4
 T2g (F) (b) 4A
2g
4
 T1g (P)

(c) 4A2g  4
 T1g (F) (d) 4T
2g(F)
4
 T1g (F)

14. Solutions of [CoCl4]2– are deep blue because
(a) it is tetrahedral anion
(b) it has d7 configuration
(c) it has electronic transition in the blue part of the spectrum
(d) of transition 4A2 (F)  4
 T1(P)

ANSWERS
1. (b) 2. (a) 3. (c) 4. (d) 5. (c) 6. (a)
7. (a) 8. (a) 9. (b) 10. (c) 11. (a) 12. (a)
13. (b) 14. (d)

Short Answer Questions


1. State and explain Leporte selection rule.
2. Calculate the term symbol for d10 arrangement of electrons.
3. Derive the term symbol for an atom with s1 configuration.
4. Give a relation to calculate the number of microstates.
5. Write the Mulliken symbol for spectroscopic terms P and D in octahedral field.
6. Arrange the following in increasing order of energy:
1S , 1D , 3P , 3P , 3P
0 2 2 0 1
7. Which out of 3P2, 3P1 and 3P0 has lowest energy?
8. Differentiate between LS coupling and jj coupling.
9. The terms of d2 configuration are 1S, 3P, 1D, 3F and 1G. Which of these has the highest energy?
10. Draw Orgel diagram for a d9 configuration in an octahedral field.

General Questions
1. (a) Why do tetrahedral complexes of an element give much more intense d-d spectra than
its octahedral complexes?
(b) Discuss the electronic spectra of [Co(H2O)6]2+ and [CoCl4]2– complexes.
2. (a) Find the ground state term for each of the following configuration:
(i) d 3 (ii) d 5 (iii) d 9

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 123

(b) What are spin multiplicity forbidden and Laporte forbidden transitions?
3. (a) What are selection rules for electronic spectra?
(b) Discuss the spectral features of Mn(II) in octahedral complexes of weak and strong
ligand fields.
(c) Write briefly about L – S coupling.
4. (a) The correlation diagram for a d2 configuration as in V3+ (aq) ion does not give simple
0 value unlike the crystal field splitting diagram. Which transition from the ground state
3T would give  value?
1g 0
(b) Define spectroscopic term. Find the terms for atoms with the following configurations:
(i) s1 (ii) s1p1 (iii) p1
(c) Discuss the absorption spectra for Co (II) octahedral and Co (II) tetrahedral complexes.
(d) Discuss the nature of electronic transitions in octahedral complexes of metal ions with
d6 (high spin) configuration.
5. (a) Calculate the ground state terms with spin multiplicity for the following octahedral ions:
V3+, Ni2+, Cu2+.
(b) What is L-S coupling? How does it help to calculate the resultant angular momentum
(J) of an atom having two electrons in a d- subshell.
(c) Draw combined Orgel diagram for d1, d 4, d 6 and d 9 complexes.
6. (a) Discuss the Orgel diagram and absorption spectra for a d 8 ion.
(b) According to Laporte selection rule, electronic transitions of the d-d type displaced in
spectra of octahedral complexes should be forbidden. Why are moderately strong spectra
actually observed?
(c) The absorption spectrum of Ti3+ (aq) (d1) is attributed to a single t2g  eg transition.
Explain the position, intensity and broad nature of this band.
7. (a) Determine the ground state term symbol of anion with d1 configuration.
(b) What is meant by spectrochemical series?
(c) Draw combined Orgel diagram for d1, d 4, d 6 and d 9 complexes.
(d) Write briefly about L – S coupling scheme of angular momenta.
8. (a) Identify the ground state term from each set of the following terms:
(i) 1S, 3P, 1D
(ii) 1S, 2P, 2D, 3F, 1G
(iii) 1S, 3P, 1D, 3F, 1G
(b) For [V(H2O)6]3+ two absorption bands are observed at 17,800 and 25,700 cm–1. Assign
these bands.
(c) Explain as to why Co(II) octahedral complexes are light pink while tetrahedral species
are intense blue in colour?
9. (a) Draw the energy level diagram for d2 configuration in tetrahedral and octahedral fields
showing three possible transitions.
(b) How does Hund’s rule help to arrange the different spectroscopic terms in order of their
increasing energies? How does it help to find the term in ground state?
(c) Name the largest energy transition for high spin octahedral complexes for V3+, Ni2+,
Cr3+, and Cu2+.
10. (a) Discuss Russel-Saunders states for d 2 configurations.
(b) Give energy level diagram and electronic spectra of Cr (III) octahedral complexes.

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
124 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

11. (a) Discuss the special features of electronic spectra of [Ni(H2O)6]2+ ion.
(b) Draw combined Orgel diagram for d1, d 4, d 6 and d 9 complexes.
12. (a) Write a short note on L-S coupling.
(b) Discuss special features of electronic spectra of Cr (III) octahedral and Mn (II)
octahedral complex ions.
13. (a) Find out the ground state terms with spin multiplicity for Cu2+ and V3+ ions.
(b) Name the factors which govern the magnitude of .
(c) Draw an Orgel diagram for d 3 in Oh complex.
14. (a) Show how one gets the following terms for d 2 configuration:
1G, 3F, 1D, 3P and 1S. Which of these belong to ground state?

(b) Will the electronic spectra of [Co(H2O)6]2+ and [CoCl4]2– be same? If not explain the
differences that one encounters.
(c) Electronic transition of the d-d type displayed in the spectra of octahedral transition metal
complexes should be forbidden by the Laporte selection rule. Why are moderately strong
spectra actually observed? Is this the reason that spectrum of [Co(H2O)6]2+ is less easy
to interpret?
15. (a) Derive Russel-Saunders states for d 2 configuration. Arrange these in accordance with
their increasing energies diagrammatically.
(b) What are Orgel diagrams? Draw and discuss the Orgel energy level diagram for
[Cu(H2O)6]2+ ion.
(c) Discuss in details the electronic spectrum of [Ti(H2O)6]3+ complex ion.
16. (a) What is L-S coupling scheme to derive the energy states of d 2 system?
(b) Discuss special features of electronic spectra of Co(II) octahedral and Co(II) tetrahedral
complex ions.
17. (a) Arrange the different spectroscopic terms of titanium with the help of Hund’s rules.
(b) Discuss the special features of the electronic spectrum of [Co(H2O)6]2+ ion.
(c) State and explain the Laporte selection rule.
18. (a) Why do tetrahedral complexes of an element give much more intense d-d specrta than
its octahedral complexes?
(b) What are the two important limitations of Orgel energy level diagrams?
19. (a) What do you understand by a term symbol? Derive the term symbols for p2-configuration
and calculate the ground state term using Hund’s rule or L-S coupling scheme.
(b) Draw combined Orgel–Energy level diagram for d1 and d 9 octahedral complexes.
20. (a) Define L–S coupling.
(b) What is spectrochemical series.
(c) Why is [Ti(H2O)6]3+ ion violet?
(d) Describe electronic spectra of [Mn(H2O)6]2+.
21. (a) Derive the term symbols for d 2 configuration.
(b) [Ti(H2O)6]3+ is purple in colour. Explain.
(c) Describe the vibronic coupling with example.
22. (a) What are Orgel diagrams? What information is conveyed by these diagrams?
(b) Give a detailed account of the selection rules of electronic spectra.

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/
ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 125

23. (a) Why do tetrahedral complexes of d-block elements give much more intense d-d spectra
than its Oh complexes?
(b) Derive the ground state term symbol for an atom with the help of L-S coupling for d2
and d6 configuration?
24. (a) Derive the term symbols for p6 and d10 systems.
(b) Draw Orgel diagram for d1 and d 9 systems.
25. (a) Discuss the nature of electronic transitions in d 6 octahedral.
(b) Tetrahedral complexes of Mn(II) are more intensely coloured than the octahedral
complexes of Mn(II) explain.
(c) Draw Orgel diagram for d1 complexes.
26. (a) Draw Orgel diagram for d1 and d9 system.
(b) State any two selection rules for electronic spectrum of transition metal complexes.
Discuss exception if any.
(c) Identify ground term assuming L–S coupling for ions.
(i) 2p2 (ii) 3d 8
27. (a) Find out the ground state term for the following octahedral ions: Cu+2, V+3 and Ni+2.
Write their multiplicity also.
(b) Draw a combined Orgel diagram for d1, d 4, d 6 and d 9 complexes in octahedral and
tetrahedral complexes.
(c) The absorption Ti3+ (aq), d1 is attributed to single (i) t2g  eg transition. Explain the
position, intensity and broad nature of the band.
28. (a) The complex [Ti(H2O)6]3+ shows a single absorption band at 20,300 cm–1, Calculate
(Crystal field splitting energy).
(b) What will be the term symbol for ground state for configuration d3.
(c) Draw Orgel diagram for d2 configuration in octahedral complexes.
29. (a) Calculate the term symbol for ground state of Cr.
(b) For [V(H2O)6]3+ two absorption bands are observed at 17780 and 25700 cm–1. Assign
these bands.
(c) State and explain Hunds rule for assigning ground state spectroscopic term with suitable
examples.
30. (a) Find the Russel-Saunders terms for p2 configuration. What will be the ground state?
Draw their splitting diagram in terms of energy.
(b) Why do tetrahedral complexes give much more intense d-d transition than octahedral
complexes?
(c) Find the ground state term for [Ti(H2O)6]3+ ion. Comment upon the colour of this
complex ion.

Created with Print2PDF. To remove this line, buy a license at: http://www.software602.com/